Coating compositions containing east india resin



Melamine-formaldehyde resin B Patented Aug. 4, 1942 COATING COMPOSITIONS CONTAINING EAST INDIA nnsnv Robert '0. Swain, Riverside, and Pierrepont Adams, Stamford, Conn., assignors to American Cyanamid Company, New York, N. Y., a corpo ration Maine No Drawing.

3 Claims.

This invention relates to coating compositions containing Pale East India resin and melamineiormaldehyde resins. An object of this invention is to improve the physical and chemical properties of coating compositions containing Pale East India resin, e. g., solvent resistance, acid resistance, water resistance, etc.

, Another object of this invention is to provide compositions containing Pale East India resin and compatible proportions of compatible melamine-formaldehyde resins. These and other objects are attained by blending Pale East India resin with up to about 60% (total solids weight basis) of a melamine-formaldehyde resin which has been alkylated with an alcohol containing at least 6 carbon atoms wherein the molal ratio of formaldehyde to melamine is at least about 4:1.

The following examples in which the proportions are in parts by weight are given by way of illustration and not in limitation.

EXAMPLE 1 I Parts Melamine-formaldehyde resin A 10 Pale East India Macassar resin 90 A composition containing these ingredients is prepared by admixing parts of melamineformaldehyde resin A solution (50% resin) with 360 parts of Pale East India resin stock solution (containing of Pale East India Macassar resin and 75% of toluene). Films of the composition are applied to metal objects and baked at a temperature of about 135 C.

for about one-half hour. The product is a hard, transparent coating having good film strength.

Exam ne 2 v v Parts Melamine-formaldehyde resin "A Pale East India Macassar resin. 50

of about 135 C. for about one-half hour. A

clear, tough mm is formed.

Exluurrs 3 Parts 5 Pale East India Macassar resin- Application November 26, 1940, Serial N0. 367,218

with 300 parts of Pale East India resin-stock solution. Films of "the composition are applied to metal objects andvbaked at a temperature of about 135 C. -for about one-half hour. The

' product formed is a very hard, clear coating.

' tion. may be diluted to about 50% solidswith p Parts Melamine-formaldehyde (molal ratio 71:4)

spray-dried powder 200 2-ethyl hexanol. 280 mButanol t 320 Methyl acid phosphate 4 Preparation of melamine-formaldehyde resin "A Parts Melamine (1 mol) 126 Formalin (5 mols) ram formaldehyde in- This mixture is placed in a reflux apparatus which is provided with a condenser and a suitable water trap through which the reflux condensate passes on its return to the reactionchamber and in which the essentially aqueous fraction of the condensate may be separated from the essentially non-aqueous fraction and means is provided so that the former fraction may be drawn off if desirable. The reaction mixture is refluxed at a temperature of about -85" C. at atmospheric pressure for 6- 12 hours. The water is removed by azeotropic distillation from the reaction mixture during the reflux operation beginning preferably aiter about 24 I hours have elapsed and the water so removed is separated from the reflux condensate in the water trap. When the refluxcondensateis'substantially anhydrous the vapor temperature will. be about 100-105 C. The pressure is lowered sufliciently to reduce the vapor temperature. to about -90 C. and the resin solution is concentrated to about 60-'70% solids by vacuum distillation. This solution is essentially a hexyl;- ated resin in hexyl alcohol, all or nearly all of the methanol having been eliminated mm it during the distillation. The resulting resin soluany desired solvent or diluent, e. gi xylen. Preparation of melamine-formaldehyde resin Bf The melamine-iormaldehyde condensation prod! not is obtained by refluxing melamine and form ratio of 1:4 at a pH of about 7-9 for about 3 with an alcohol.

hours and then spray-drying. Our products may be plasticized with a wide The spray-dried melamine-formaldehyde powvariety of materials such as the alkyl phthalates,

der, octanol, butanol and methyl acid phosphate 6 tricresyl phosphate, various alkyd resins, parand refluxed about 30 minutes. This solution is etc.

a product containing about 50% solids; be added to our compositions, e. g., lithopone, Alkylated melamine-formaldehyde resins may 10 zinc oxide, titanium oxide, .ferric oxide, Prussian be produced in accordance with the procedures blue, toluidine red, malachite green, mica, glass outlined above, as well as in any other suitable fibers, ground glass, powdered silica, etc.

manner. Aqueous syrups of melamine-formal- Curing catalysts may be incorporated in the dehyde resins may be first produced and then compositions to eil'ect a more rapid 6 118 01' e alkylated either simultaneously with dehydramelamine-formaldehyde resins or to enable the tion or subsequent to dehydration. Generally resin to be cured at lower temperatures than inthe simultaneous condensation of melamine, dicated in the above examples. Such substances formaldehyde and a suitable alcohol is used beare, for instance, phosphoric acid, ammonhnn cause of convenience. In order to facilitate the salts of phosphoric acid, etc.

alkylation with the higher alcohols required in 2 Other resinous compositions may be included the above examples, e. g., hexyl alcohols and the in various coating o positi s, 8; moctanols, a low boiling alcohol such as methanol aldehyde resins, phenol-formaldehyde resins, or butanol may be mixed with the higher alcoalkyd resins, ethyl cellulose, cellulose acetate, hol, thereby assisting in removing the water and nitrocellulose, etc., as well as in varnishes, espee causing the reaction to take place readily at cially drying oil varnishes such as those from somewhat lower temperatures than would othertung oil, linseed oil, etc.

wise be required. The low boiling alcohol is re- Our mixed products show improved chemical moved by-distillation after the reaction is comresistance, solvent resistance and are much less pleted. Another method for producing resins .thermoplastic than Pale East India resin comalkylated with a higher alcohol is to alkylate the 3 positions not containing melamine-formaldehyde melamine-formaldehyde resin with a low boi1-' resins.

ing alcohol such as methanol and subsequently Our compositions are useful in the manufacreplacing it withthe desired higher alcohol, disture of paints and varnishes, as well as in lactilling out the low boiling alcohol. The condenquers, printing inks, adhesives and miscellaneous sation may be carried out either with or without decorative and p otective co g composition!- an acid catalyst and in some instances basic cata- Our products are useful in coating and impreglysts may desirably beutilized. nating paper and cloth for various purposes.

The melamine-formaldehyde resins vary slight- Our products-are particularly suitable for the lyaccording to minor variations in control durproduction of varnishes and paints having a ing their production and in some instances small 40 high gloss. proportions of a suitable solvent material, e. g., The term compatible as used herein is in toluene, benzene, xylene, turpentine, petroleum tended to denote compositions, films of which are hydrocarbons, ethyl ether, etc., may be added to clear and homogeneous after bakin the original solutions of Pale East India resin Obviously many modifications and variations and melamine-formaldehyde resin in order to in the processes and compositions described produce perfectly clear solutions if such soluabove may be made without departing from the tions are not originally obtained. spirit and scope of the invention as deilned in 7 While formaldehyde has been used in the prethe appended claims.

vious examples, it will be obvious that the vari- We claim:

ous polymers of formaldehyde, e. g., paraform- 1. A coating composition containing Pale East aldehyde,'or substances which yield formalde- India resin and a substantial proportion of a hyde may be used in place of part or all of the melamine-formaldehyde resin which has been formaldehyde. alkylated with an alcohol containing at least 6 As indicated by the above examples Pale East carbon atoms, wherein the molal ration of form- India resin has been found to be compatible with aldehyde to melamine is at least about 4:1gand up to about of melamine-formaldehyde wherein the weight ratio of melamine-formalderesins wherein the molal ratio of formaldehyde hyde resin to East India resin is up to about 3:2. to melamine is at least about 4:1. Melamine 2. A coating composition containing Pale East resins which have been alkylated with benzyl India resin and a substantial proportion of a .alcohol and wherein the molal ratio of 'i'ormal- 60 melamine-formaldehyde resin which has been dehyde to melamine is about 5:1 are compatible alkylated with n-hexyl alcohol wherein the molal with Pale East India resin in proportions not ratio of formaldehyde to melamine is at least greater than 20% of the former. While higher about 4:1 and wherein the weight ratio of meljratios of formaldehyde to melamine than 6:1 amine-formaldehyde resin to East Indiaresin is may be used, it is generally undesirable inasmuch up to about 3:2. as formaldehyde is lost during the curing so that 3. A coating composition containing Pale East the product in its cured condition does India resin and a substantial proportion of a not contain more than about 6 mols of formaldemelamine-formaldehyde resin which has been hyde to 1 mol of melamine. The percentage alkylated with 2-ethyl hexanol wherein the molal composition in each instance in the last pararatio of formaldehyde to melamine is at least graph is on a total solids weight basis. about 4:1 and wherein the weight ratio of meistraight chain or branched chain alcohols con- 7 .up toabout 3:2. .7 taining at least 6 carbon atoms. The term al- ROBERT C. SWAIN. kylated melamine-formaldehyde resin is intend- PIERREPONT ADAMS.

alin (37% formaldehyde in water) the molal ed to denote compositionsv which are reacted are 'heated to about -105 0. in 30 minutes ticularly the fatty oil acid modified alkyd resins,

vacuum concentrated at about 50 -70 C. to form Various fillers, pigments dyes and lakes may The resins maybe alkylated with any of the amine-formaldehyde resin to East India resin is P 

